Acylated derivatives of 2,6-dihydroxy-9-azabicyclo (3.3.1)nonane

ABSTRACT

Compounds having the formula   WHEREIN R1 is hydrogen, alkyl or benzyl and R2 is alkyl, benzyl or a hindered phenolic group ARE GOOD LIGHT STABILIZERS AND ANTIOXIDANTS. These compounds are prepared by reacting 2,6-dihydroxy-9-azabicyclo(3.3.1)nonane with an appropriate carboxylic acid.

United States Patent [191 Stephen [451 Oct. 14, 1975 ACYLATED DERIVATIVES OF 2,6-DIHYDROXY-9-AZABICYCLO [3.3.1]NONANE [75] Inventor: John F. Stephen, New City, NY.

[73] Assignee: Ciba-Geigy Corporation, Ardsley,

22 Filed: Jan. 14,1974

21 Appl. No.: 433,421

[52] US. Cl 260/293.54; 260/45.8 N [51] Int. Cl. C07D 221/22 [58] Field of Search 260/293.54

[56] References Cited OTHER PUBLICATIONS Portmann et al., Helv. Chim. Acta, 56(6), 1991-2007 (1973).

Primary Examiner-G. Thomas Todd Attorney, Agent, or Firm-Charles W. Vanecek; Nestor W. Shust [57] ABSTRACT Compounds having the formula i 2 OCR R CO wherein R is hydrogen, alkyl or benzyl and R is alkyl, benzyl or a hindered phenolic group are good light stabilizers and antioxidants. These compounds are prepared by reacting 2,6-dihydroxy-9- azabicyclo[3.3.l]nonane with an appropriate carboxylic acid.

14 Claims, No Drawings ACYLATED DERIVATIVES or 2,6-DIHYDROXY-9-AZABICYCLO [3.3.1]NONANE DETAILED DISCLOSURE This invention relates to compounds and organic compositions stabilized therewith. More specifically, these compounds are useful as stabilizers of organic materials which are subject to thermal, oxidative and ultraviolet light degradation; The novel compounds can be represented by the formula ocR wherein R is hydrogen, alkyl having 1 to 12 carbons or benzyl and l R is alkyl having 1 to 24 carbons, benzyl, alkyl substituted benzyl, or a hindered phenolic group having the formula wherein R and R are lower alkyl having 1 to 8 carbon atoms,

and 1 x is 'an integer of 0 to 2.

2 ing compounds are particularly good antioxidant and thermal stabilizers.

' Esters of 2,6-dihydroxy-9-azabicyclo[3.3.l]nonane can be prepared by reacting 2,6-dihydroxy-9-azabicyclo[3.3.1]nonane with the appropriate carboxylic acid in a suitable solvent, for example, xylene, in the presence of a titanium tetra-alcoholate catalyst such as titanium tetra-isopropylate. 2,6-dihydroxy-9-azabicyclo[3.3.l1nonane can be prepared from 5,10-dioxatricyclo[7.l.0.0"' ]decane which can be prepared according I to the method described in U.S. Pat. No.

*Esters of 9-substituted-2,6-dihydroxy-9-azabicy clo[3.3.l1nonane can be prepared by reacting the isomericmixture ofdiols which results from the reaction of 5, l 0dioxatricyclo[7 l .0.0-]decane with the appropriate primary amine with the appropriate ,carboxylic acid in a suitable solvent such as xylene in thepresence of titanium tetra-alcoholate catalyst such. as titanium tetraisopropylate. The mixture of diols above consists of the 9'substituted-2,6-dihydroxy-9-azabicyclo[ 3.3. 1- ]nonane and the corresponding 9-substituted-2,5-dihydroxy-9-,azabicyclo[4.2. l ]nonane in about equal amounts. The [4.2. I ]ring system in the 9-substituted- 2,5-dihydroxy-9-azabicyclo[4.2. l ]nonane rearranges to the [3.3.1] system during esterification. illustrative examples of the compounds of this invention are:

The preferred embodiment of the above represented compounds is where R is hydrogen, lower alkyl having 1 to 4 carbons and benzyl, and where R is alkyl having from 1 to 17 carbons, benzyl or the group where .x is zero, one or 2 and R and .Rf are branched alkyl such as .isopropyl, secand tert-butyl, secand tert-amyl, secand tert-heptyl or secand tert-octyl. Most preferably said groups are tertbutyL,

It should be noted that when Riis alkyl, benzyl, alkyl substituted benzyl or a hindered phenolic group where the integer ,r is zero, the resulting compounds are good ultraviolet light stabilizers. However, whenR is a hindered phenolic group where x is one or two, the result- 2,6-diacetoxy-9-azabicyclo[ 3 3. l ]nonane 2,6-diacetoxy-9-butyl-9-azabicyclo[ 3 .3. l ]nonane 2,6-distearoyloxy-9-butyl-9-azabicyclo[3.3.l ]nonane 1 2,6-diacetoxy-9-benzyl-9-azabicyclo[ 3 .3. l ]nonane 2,6-distearoyloxy-9-benzyl-9-azabicyclo[3.3.11nonane.

EXAMPLE I 5, l0-Dioxatricyclo[ 7. l .0.0 ]decane 5 ,10Dioxatricyclo[7. 1 .0.0- ]decane was prepared following the procedure described in U.S. Pat. No. 3,241,979 a solution of sodium acetate (163.0 g.) in 40% peracetic acid (1315.0 g.) wasadded dropwise during 2.5 hours to vigorously stirred 1,5-cyclooctadiene (275.3 g.). During the addition the temperature was kept below 25 by use of an ice bath. After the addition was completed the mixture was cooled to 0 and kept at 0' for about 20 hours. The pH of the mixture was adjusted to 11 by the addition of potassium hydroxide solution. The mixture was extracted with 4.5 litres of ether, and the dried (Na SO ether solution was evaporated under reduced pressure to give 294.0 g.

of a colorless oil. Distillation through a 3-foot spinning band column gave 200 g. of pure 5,10dioxatricyclo [7.l.0.0,"]-decane, b.p. 56/0.1 mm. which solidified on standing.

y EXAMPLE 2 l 2,6-Dihydroxy 9-Azabicyclo[3.3.l]nonane 3 tion of dioxane to the filtrate produced a second crop of material. The combined crops were recrystalliied from methanol to give 31.0 g. of the title compound, m.p. 243245. Concentration of the mother liquor af- 4 Treatment of this mixture with butyric acid and titanium tetraisopropylate as in Example 3 gave the title compound as an oil. i a

Analysis Calculated for C H NO forded asecond crop of 14.0 g. m.p. 235238. 5 7o Calculated: C, 67.95; H, 9.98; N, 3.96.

. 70 Found: C, 67.76; H, 10.05; N, 3.94. EXAMPLE 3 v The compounds listed in Table l were prepared ac- 2,6-Dibutyryloxy9-Methyl-9-Azabicyclo[3.3. 1 ]nocording to the procedure of Example 3. y

I nane L g A Fischer and Porter-pressure bottle was charged 10 Table I with 5,l0-dioxatricyclo[7.l.0.()*"]decane (28.0 gm, 0.2 mole), 50 ml. of ethanol and 40% aqueous methyl- Acylated Derivatives of amine (62.0 g., 0.8 mole). The mixture was heated at '2 ,6'-Dihydroxy-9'- Az abicy'c'l0 l40-l50 for 12 hours. Ethanol, water and excess me- 1 5 thylamine were removed under reduced pressure to M give an oily residue. Recrystallization from acetone gave 31.1 g. of a 1:1 mixture (as determined by analysis of the NMR spectrum of the mixture) of 2,6-dihydroxy- 9-methyl-9-azabicyclo[3.3.l ]nonane and 2,5-dihy- 2O droxy-9-methyl-Q-azabicyclo[ 3.3.] nonane m.p. 130 162". I I To a stirred solution of the diol mixture, 2,6-dihydroxy-9-methyl-9-azabicyclo[3.3. l ]nonane and 2,5- dihydroxy-9-methyl-9-azabicyclo[4.2. l ]nonane (5.14 g.,'0.03 mole) and butyric acid l 1.6 g., 0.132 mole) in 150 ml. of dry xylene was added 0.85 ml. of titanium tetraisopropylate. The mixture was heated under reflux for l5 hours water being removed with a Dean-Stark trap. Xylene and excess butyric acid were evaporated under reduced pressure. The oily residue thus obtained was dissolved in ether. Water was added and the mixture was stirred vigorously for about 10 minutes. The

Example No. RI R2 5 CH,, CH,, b.p. l00-|02C/0.o| mm 6 CH;I nC-,-H, oil 7 nC..H... m.p. GI-64C s CH.! Gri -Q oil 9 (CH,);,CH;, nC H on H) CHEQ nC;,H oil l l C nC H oil 12 H nC H oil 13 H nC H m.p. 6466C Each compound that was an oil was purified by chromatography over silica gel. The microanalytical results for hydrogen, carbon and nitrogen corresponded to the calculated values.

precipitated solid was filtered off, the ether layer was separated, washed with 2N sodium hydroxide solution then brine and finally dried over NA SO Evaporation of the ether gave 8.5 g. of an oil which was distilled .under reduced pressure to give 6.4 g. of the above named compound, b.p. l32l34/0.02rnm.

EXAMPLE 4 2,6-Dibutyryloxy-9-Butyl-9-azabicyclo 3.3. l ]nonane Under similar conditions, as in Example 3, reaction of 5,lO-dioxatricyclo[7.l.O.0 "]decane with n-butylamine led to a mixture of the corresponding isomeric 9- butyl-2,6-dihydroxy-9-azabicyclo[ 3.3. l ]nonane and 9-butyl-2,5-dihydroxy-9-azabicyclo[4.2. l ]nonane.

EXAMPLE l4 2,6-bis 3-(3,5-di-tert-butyl-4-hydroxy phenyl )-propionyloxy} -9-methyl-9-azabicyclo[ 3 .3. l-

. ]nonane r r residue thus obtained was dissolved in ether. The ether solution was washed with 5% aqueous sodium hydroxide and then water. The dried (Na SO solution was evaporated under reduced pressure to give an oily residue which was crystallized from petroleum ether. Recrystallization from methanol gave 9.8 g (56.6%) of the title ester, m.p. lO7-109.

EXAMPLE 2,6-bis( 3 ,5-di-tert-butyl-4-hydroxyphenylacetoxy )9- methyl-9-azabicyclo[3.3.1.]nonane Under nitrogen a stirred solution of the diol mixture 2,6-dihydroxy-9-methyl-9-azabicyclo[ 3.3. l jnonane and 2,5-dihydroxy-9-methyl-9-azabicyclo[4.2. 1 ]nonane (4.28 g, 0.025 mole), 3,5-ditert-butyl-4-hydroxyphenylacetic acid (14.55 g, 0.055 mole) and titanium tetraisopropylate (0.7 ml) in 100 ml of xylene was heated under reflux for 18 hours water being removed with a Dean-Stark trap. The xylene was evaporated under reduced pressure and the residue was dissolved in ether. The ether solution was washed with water then 10% aqueous sodium hydroxideand again with water. The dried (Na SO solution was crystallized from petroleum ether and then from hexane to give 4.6 g (28%) of the desired ester, m.p. 98-l0OC.

EXAMPLE 16 vinyl halides with unsaturated polymerizable compounds, e.g., vinyl esters, a, B-unsaturated acids, 0:, B- unsaturated esters, a, ,B-unsaturated ketones, a, ,B- unsaturated aldehydes and unsaturated hydrocarbons such as butadienes and styrene; poly-a-olefins such as high and low density polyethylene, crosslinked polyethylene, polypropylene, poly(4-methylpentene-1 and the like, including copolymers of a-olefins; such as ethylene-propylene copolymers, and the like; dienes such as polybutadine, polyisoprene, and the like, in

cluding copolymers with other monomers; polyurethanes such as are prepared from polyols and organic polyisocyanates, and polyamides such as polyhexamethylene adiparnide and polycaprolactam; polyesters such as polyethylene terephthalates; polycarbonates such as those prepared'from bisphenol-A and phosgene; polyacetals suchas polyethylene terephthalate polyacetal; polystyrene, polyethyleneoxide; polyacrylics such as polyacrylonitrile; polyphenyleneoxides such as those prepared from 2,6-dimethylphenol and the like; and copolymers such as those of polystyrene containing copolymers of butadiene and styrene and those formed by the copolymerization of acrylonitri1e,butadiene and/or styrene. I

' Other materials which can be stabilized by the compounds of the present invention include lubricating oil of the aliphatic ester type, i.e., di(l,2-ethylene)-azelate, pentaerythritol tetracaproate, and the like; animal and vegetable derived oils, e.g., linseed oil, fat, tallow, lard, peanut oil, cod liver oil, castor oil, palm oil, corn oil, cottonseed oil, and the like; hydrocarbon materials such as gasoline, mineral oil, fuel oil, drying oil, cutting fluids, waxes, resins, and the like, salts of fatty acids such as soaps and the like; and alkylene glycols, e.g., ,B-methoxyethyleneglycol, methoxytriethyleneglycol, triethylene glycol, octaethyleneglycol, dibutyleneglycol, dipropyleneglycol and the like.

The compounds of this invention are particularly useful as UV light stabilizers and as antioxidants, especially for the protection of polyolefins, for instance, polyethylene, polypropylene, poly( butene-l poly(- pentene-l), poly(3-methylbutene-l), poly(4-methylpentene-l various ethylene-propylene copolymers and the like.

In general, the stabilizers of this invention are employed from about 0.01 to about 5% by weight of the stabilized composition, although this will vary with the particular substrate and application. An advantageous range is from about 0.05 to about 2% and especially 0.1 to about 1%.

For addition to polymeric substrates, the stabilizers can be blended before polymerization or after polymerization, during the usual processing operations, for example, by hot-milling, the composition then being extruded, pressed, blow molded or the like into films, fibers, filaments, hollow spheres and the like. The heat stabilizing properties of these compounds may advantageously stabilize the polymer against degradation during such processing at the high temperature generally encountered. The stabilizers can also be dissolved in suitable solvents and sprayed on the surface of films, fabrics, filaments or the like to provide effective stabilization. Where the polymer is prepared from a liquid monomer as in the case of styrene, the stabilizer may be dispersed or dissolved in the monomer prior to polymerization or curing.

These compounds can also'be used in combination with other additives such as antioxidants, sulfurcontaining esters such as distearyl-/3-thiodipropionate (DSTDP), dilauryl-B-thiodipropionate (DLTDP) in an amount of from 0.01 to 2% by weight of the organic material, and the like, pourpoint depressants, corrosion and rust inhibitors, dispersing agents, demulsifiers, antifoaming agents, fillers such as glass or other fibers, carbon black, accelerators and the other chemicals used in rubber compounding, plasticizers, color stabilizers, diand tri-alkyland alkylphenylphosphites, heat stabilizers, ultraviolet light stabilizers, antiozonants, dyes, pigments, metal chelating agents, dyesites and the like. Often combinations such as these, particularly the sulfur containing esters, the phosphites and/or the ultraviolet light stabilizers will produce superior results in certain applications to those expected by the properties of the individual components.

The following formula represents co-stabilizers which are in certain instances very useful in combination with the stabilizers of this invention:

wherein R is an alkyl group having from 6 to 24 carbon atoms; and n is an integer from 1 to 6. Especially useful compounds of this type are dilauryl-B-thiodipropionate and distearyl-B-thiodipropionate. The above co-stabilizers are used in the'amount of from 0.01 to 2% by weight of the organic material, and preferably from 0.1 to 1%.

Although the compounds of this invention may to some degree also be effective thermal stabilizers, if the processing of the polymer is carried out at high temperaturesit is advantageous to incorporate additional antioxidants.

In most applications, it is desirable to incorporate into the resin composition, sufficient thermal antioxidants to protect the plastic against thermal and oxidative degradation. The amount of antioxidant required will-becomparablc to that of the actinic stabilizer. Namely, from about'0.005 to and preferably from 0.01 to 2% by weight Representative of such antioxidants are phosphite esters, such as triphcnylphosphite and dibutylphosphite and alkyl arylphosphites such as dibutylphenylphosphite, and the like.

- 'The best results have been obtained with the preferred class of thermal antioxidants, the hindered phenols. These compounds have been found to provide the best thermal stabilization with the least discoloration in the compositions of the invention. Among these phenolic antioxidants are includedthe following:

di-n-octadecyl( 3-5-butyl-4-hydroxy-5 -methylbenv zyl)malonate 2,6-di-t-butylphenol 2,2 -methylene-bis( 6-t-butyl-4-methylphenol) 2,6 di-t-butylhydroquinone octadecyl-(B ,5-di-t-butyl-4-hydroxybenzylthio)ace- I tate l l ,3-tris( 3-t-butyl-6-methyl-4-hydroxyphenyl )butane 1,4-bis( 3 ,5-di-t-butyl-4-hydroxybenzyl )-2,3-5,6-tetramethylbenzene 2,4-bis-(3,5 di-t-butyl-4-hydroxyphenoxy)-6-(noctylthio)- l ,3 ,5 -triazine 2,4-bis-(4-hydroxy-3,S-di-t-butylphenoxy)-6-( noctylthioethy1thio)- l ,3,5-triazine 2 ,4-bis-( n-octylthio )-6-( 3 ,5-di-t-butyl-4-hydroxyanilino)*1,3,5-triazine 2,4,6-tris-(4-hydroxy-3,5-

di-t-butylphenoxy l',3 ,5-triazine n-octadecyl-,8( 3 ,S-di-t-butyl-4-hydroxyphenyl )propionate n-octadecyl-3,5-di t-butyl-4-hydroxybenzoate 2-(n-oetylthio)ethyl3,5-di-t-butyl-4-hydroxybenzoate stearamido N,N-bis-ethylene N,N-bis-{ethylene- (3 ,5 -di-t-butyl-4-hydroxyphenol)propionate} 1,2-propylene glycol bis-{3-(3,5-di-t-butyl-4-hydroxyphenyl )propionate'} 1 pentaerythritol tetrakis- {3-( 3,5-di-t-butyl-4-hydroxphenyl)propionat'e dioctadecyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate di-n-octadecyll 3 ,5-di-t-butyl-4-hydroxyphenyl ethanephosphonate.

The above phenolic hydrocarbon stabilizers are known and many are commercially available.

The above antioxidants have been listed only for the purpose of illustration and it is important to note that any other antioxidant can be employed with similar im- ARTIFICIAL LIGHT EXPOSURE TEST Deterioration of most polymers caused by ultraviolet light is so slow at ambient temperatures, even in the absence of stabilizers, that testing of the effects of stabilizproved results. The above exemplified antioxidants and ers generally must be conducted either at higher temperatures or in an accelerated aritifical light exposure device in order to yield results in a convenient period of time. The tests conducted on polymers using an artificial light exposure device is described below:

a. Sample Preparation 5 mil Film Unstabilized polypropylene powder (Hercules Profax 650i) is thoroughly blended with the indicated amounts of additives. The blended material is then milled on a two roll mill for 5 minutes at 182C. The milled sheet is then compression molded at 220C into 5 mil thick film under a pressure of psi and water cooled in the press.

b. Testing Method This test is conducted in a FS/BL unit, basicallyof the American Cyanamid design, which consists of 40 tubes of alternating fluorescent sunlamps and black lights (20 of each). The 5 mil sample film which are mounted on a 3 X 2 inches IR card holders with A1. 1 inch windows and are placed on a rotating drum 2 inches from the bulbs in the FS/BL unit. The time in hours is noted for the development of 0.5 carbonyl absorbance units as determined on an Infrared Spectrophotometer.-The development of carbonyl functional groups in the polymer is proportional to the amount of degradation caused by the ultraviolet light exposure.

The test results reported below were obtained according to the procedures described above. The amounts of the additives are expressed in weight per cent based on the weight of the polymer.

Table II Light Stabilization Data in Polypropylene Time in Hours to 0.5 Carbonyl Table ll-continued Light Stabilization Data in Polypropylene Time in Hours to 0.5 Carbonyl Example No. Stabilizer Absorbance Units 27 Compound of Example 11 460 875 28 None .230 555 Formulation A The composition contains 0.5% of the indicated suibilizcr and 0.2% of di'n-octadccyl (3.S-di-t-butyl-4-hydroxybcnzyl)phosphonatc which is an antioxidant which prevents oxidativc degradation of polypropylene.

I Formulation B The composition contains 0.25% of the indicated stabilizer.

0.257: of UV absorber 2( 2' hydroxy-3'.5'-di-t-butylphcnyl )--chlorohcnzotrialole and 0.2% of antioxidant din-octadecylt3.5-di-tcrt-hutyI-4-hydroxybenzyl)phosphonatc.

The compositions of Table 11 are equally stabilized when 2 {2 -hydroxy-3 ,5 -di-t-butylphenyl} -5- chlorobenzotriazole is replaced with the following UV absorbers:

a. 2-hydroxy-4-methoxy-5-sulfobenzophenone -trihydrate b. 2-hydroxy-4-n-octoxybenzophenone c. {2,2'-thiobis( 4-t-octylphenolate)} -n-butylamine I EXAMPLE 29 Pellets (500 g) of unstabilized nylon-6,6 (Zytel 101, DuPont) are placed in a Kitchen Aid Mixer. With mixing a solution of 0.5% (based on the weight of nylon) of 2,6-distearoyloxy-9 azabicyclo[3.3.1]nonane in 20 ml of methylene chloride is added slowly. Sodium hypophosphite (0.5 gm. 0.1%) is dissolved in 20 ml of water and added slowly with mixing to the nylon pellets after the antioxidant solution has been added and most of the methylene chloride has evaporated. The stabilized pellets are dried at 80C at l mm Hg. for 4 hours.

The polyamide formulation is extruded at 600F through at A inches die into a rod which is water cooled and chopped into pellets. A A inch Brabender extruder, equipped with a nylon screw, is used. The pellets are dried at 80C at l mm for 4 hours.

The dried pellets are reextruded into 5 mil (nominal) monofilament fiber which is subsequently oriented (4:1). The oriented fibers are exposed to outdoor weathering (direct and under glass) and tensile measurement is made periodically. The sample is considered to have failed when it loses 50% of its original tenacity. The sample stabilized with the above noted EXAMPLE 30 Unstabilized high impact polystyrene resin is dry blended with 0.01% by weightof the resin of 2,6dioctanoyloxy-9-azabicyclo[3.3. 1 ]nonane. The resin is then extrusioncompounded on a 1 inch 24/ 1=L/D extruder, melt temperature 500F and pressed for 7 minutes at a temperature of 163C and a pressure of 2000 psi into a sheet of uniform thickness of mil. The sheets are then cut into plaques of 2 X 2 inch. The plaques are then exposed in a FS/BL exposure device and color measurements made periodically using a Hunter Color Difference Meter Model D25. The polystyrene samples stabilized with the above ester developed the undesirable yellowjdiscoloration substantially later after such discoloration occurred in the unstabilized samples.

EXAMPLE 3 l Unstabilized linear polyethylene is solvent blended in methylene chloride with 0.5% by weight of the substrate of I 2,6-dioctanoyloxy-9-methyl-9-azabicyclo [3.3.1]-nonane and then vacuum dried. The resin is then extruded at 450F as described in Example 29. Thereafter, the test procedure of Example 28 is followed and the light stability of the samples determined. Polyethylene stabilized with the above ester is found to be much more stable than the unstabilized polyethylene or the polyethylene stabilized only with an antioxidant.

EXAMPLE 32 A quantity of SBR emulsion containing 100 g of rubber (500 ml of 20% SBR obtained from Texas U.S., Synpol 1500) previously stored under nitrogen, is placed in a breaker and stirred vigorously. The pH of the emulsion is adjusted to 10.5 with a 0.5N NaOH solution.

To the emulsion is added 50 ml of 25% NaCl solution. A 6% NaCl solution adjusted with hydrochloric acid to a pH 1.5 is added in a thin stream with vigorous stirring. When pH 6.5 is reached, the rubber begins to coagulate and the addition is slowed down in order to maintain uniform agitation. The addition of the acidic 6% solution isterminated when a pH 3.5 is reached. The coagulated crumbrubber slurry at pH 3.5 is stirred for 12 hour. 7

The coagulated rubber is isolated by filtration through cheese cloth, and rinsed with distilled water. After three subsequent washings with fresh distilled water, the coagulated rubber is dried, first at 25 mm Hg and finally to constant weight under high vacuum 1 mm at 40-45C.

The dried rubber (25 g) is heated under nitrogen at C in a Brabender mixer and to this is added with mixing 0.5% of 2,6-dibutyryloxy-9-methyl-9-azabicyclo[3.3. 1 ]nonane. The composition is mixed for 5 minutes after which it is cooled and compression molded at 125C into 5 X 0.025 inch plaques.

The plaques are exposed to a xenon arc weatherometer and the color measurement (L-b) is made after 45, 125 and 290 hours. The samples stabilized with the above ester is found to be much more light stable than the unstabilized samples.

' EXAMPLE 33 7 To 50 g of polyacetal resin containing 0.1% of an acid scavenger, dicyandiamide, is added 0.2% by weight of 2,6-butyryloxy-9-butyl-9-azabicyclo[3.3.1]-

nonane, and milled for 7 minutes at 200C in a Bra bender Plastirecorder. The milled formulation is subse- 350 psi. The stabilized sheets are then remolded for 2 minutes at contact pressure and for 3 minutes at 300 II 2 psi at2l5C to give plaques 1 /2 x 2% inch X 125 mil. OCR Thereafter, the testing procedure of Example 28 is followed to determine the light stability of the samples. 5 Q The stabilized samples are found to be much more stable than the Unstabilized samples.

R (50 EXAMPLE 34 l0 0 Unstabilized thoroughly dried polyethylene terewherfiln phthalate chips are dry blended with 1.0% of 2,6-dioc- Is hydrogen, alkyl having 1 to 12 carbons and tanoyloxy-9-butyl-9-azabicyclo[3.3.l ]nonane. 60/ I0 and denier multifilament is melt spun at a melt temperature I R 15 alkyl having 1 to 24 carbons. benzyl, or a hmof 290C. The oriented fiber is wound on white cards dered phenolic g p ing h orm l and exposed in a Xenon Arc Fadeometer. Color mea- 3 surements are made periodically with a Hunter Color R Difference Meter Model D25. The stabilized samples are found to be much more light stable than the unsta- (CH2) OH blhzed samples. 3

EXAMPLE 35 Unstabilized polypropylene powder (Hercules Profax 25 6501 was thoroughly blended with the stabilizers indicated in Table lll below. The blended materials were then milled on a two-roll mill at 182C for l0 minutes, after which time the stabilized polypropylene was sheeted from the mill and allowed to cool.

The milled polypropylene sheets were then cut into wherein R" and R are lower alkyl having I to 8'carbons'and x is an integer of 0 to 2.

2. A compound of claim 1 wherein R is hydrogen, alkyl having 1 to 4 carbons and benzyl, and R is alkyl having l to 17 carbons and benzyl.

3. A compound of claim 2 wherein both R and R are alkyl. i pieces and pressed for 7 mmutes on a hydraulic press at 4. A compound of claim 2 wherein R1 is alkyl and 2 218C, 2,000 pounds per square inch pressure. The rek benzy] sulting plaques of 25 mil thicltness were tested for resis- 5. A Compound of claim 2 wherein 1 is benzyl and tance to accelerated aging in a forced draft oven at R2 is alkylt 150C. When the plaques showed the first signs of decomposition (e.g., cracking or brown edges) they were considered to have failed. The results were as follows:

6. A compound of claim 2 wherein R is hydrogen and R is alkyl.

7. The compound of claim 1 which is 2,6-di-noctanoyloxy-9-benzyl-9-azabicyclo[ 3.3. l ]nonane.

8. The compound of claim 1 which is 2,6-butyryloxy- TABLE [I] 9-methyl-9-azabicyclo[3.3.l ]nonane. Oven Agingof Polypropylene 9. The compound of claim 1 which is 2,6-di-n- Time to Failure in Hour5 octanoyloxy-9-methyl-9-azabicyclo[3.3. l ]nonane.

10. The compound of claim 1 which is 2,6-di-n- Stabilizer Fomtulations A] B C, octanoyloxy-9-butyl-9-azabicyclo[3.3. l ]nonane. Q P of 14 860 850 870 11. The compound of claim 1 which is 2,6-bis- {3- 670 3 680 3,5-di-tert-butyl-4-hydroxyphenyl)-propionyloxy}-9- methyl-9-azabicyclo[3.3. l ]nonane. Formulation A contains 0.2 .4 it the indi t -d st: hili'. of th'.- i w t' 1 Formulation B contains 0.2% of the indicaititlstahilizci' zind 0.5 24 :Hlv ii bsorhcr 5O The compound of claim I which Is 26-blS-(35- 2t Z-hydroxy-3.5'-di-tcrt-hutylphcnyl )-5-chlorubcnzotriazolc. dl-tert-butyl-4-hydroxyphenylacetoxy )-9-methyl-9- Formulation C contains 0.171 of the indicated stabilizer and 0.3% of dilauryllhibi y l ]nonane. 13. The compound of claim 1 which is 2,6-bis-(3,5-

v di-tert-butyl-4-hydroxybenzoyloxy)-9-methyl-9- azabicyclo[3.3. l ]nonane. What is claimed is: 14. The compound of claim 1 which is 2,6-di-nl. A compound having the formula butyryloxy-9-butyl-9-azabicyclo[3.3. l ]nonane. 

1. A COMPOUND HAVING THE FORMULA
 2. A compound of claim 1 wherein R1 is hydrogen, alkyl having 1 to 4 carbons and benzyl, and R2 is alkyl having 1 to 17 carbons and benzyl.
 3. A compound of claim 2 wherein both R1 and R2 are alkyl.
 4. A compound of claim 2 wherein R1 is alkyl and R2 is benzyl.
 5. A compound of claim 2 wherein R1 is benzyl and R2 is alkyl.
 6. A compound of claim 2 wherein R1 is hydrogen and R2 is alkyl.
 7. The compound of claim 1 which is 2,6-di-n-octanoyloxy-9-benzyl-9-azabicyclo(3.3.1)nonane.
 8. The compound of claim 1 which is 2,6-butyryloxy-9-methyl-9-azabicyclo(3.3.1)nonane.
 9. The compound of claim 1 which is 2,6-di-n-octanoyloxy-9-methyl-9-azabicyclo(3.3.1)nonane.
 10. The compound of claim 1 which is 2,6-di-n-octanoyloxy-9-butyl-9-azabicyclo(3.3.1)nonane.
 11. The compound of claim 1 which is 2,6-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionyloxy)-9-methyl-9 -azabicyclo(3.3.1)nonane.
 12. The compound of claim 1 which is 2,6-bis-(3,5-di-tert-butyl-4-hydroxyphenylacetoxy)-9-methyl-9 -azabicyclo(3.3.1)nonane.
 13. The compound of claim 1 which is 2,6-bis-(3,5-di-tert-butyl-4-hydroxybenzoyloxy)-9-methyl-9 -azabicyclo(3.3.1)nonane.
 14. The compound of claim 1 which is 2,6-di-n-butyryloxy-9-butyl-9-azabicyclo(3.3.1)nonane. 